Process for treating textile materials



United States Patent Ofiice 3,247,913 Patented Apr. 19, 1966 3,247,013PROQIESS FOR TREATlNt'} TEXTILE MATERIALS Walter Hagge and J oseiBusing, Leverlrusen, and Joachim Kolbe, Cologne-Flittard, Germany,assiguors to Farheniabriiren Bayer Airtiengesellschaft, Leverkusen,Germany, a German corporation No Drawing. Filed Oct. 22, 1962, filer.No. 232,275 Claims priority, appiication Germany, Oct. 25, 1961,

10 Claims. 61. 117 139.5

The present invention relates to the treatment of textile materials;more particularly it concerns a process in which the textile materialsare treated with reaction products prepared by reacting (A) esters ofhigher fatty acids containing 12 to 20 carbon atoms condensed withalcohols containing 4 to 12 carbon atoms and/or polyhydric alcoholscontaining 2 to 6 hydroxyl groups with (B) amide amines in the form ofsalts or quaternization products, such as are obtainable by the action1-l.7 mole of a carboxylic acid containing 62() carbon atoms or afunctional derivative thereof on 1 mol of a diamine of the formula inwhich R and R stand independently from one another for an alkyl radicalcontaining 1 to 8 carbon atoms and n is a number from 2-4, the amount ofdiamine employed being not more than 8 percent by weight of the reactionproduct.

As esters on which the reaction products to be used according to thepresent invention can be based, there may be mentioned, for example,tallow, coconut fat, olive oil, castor oil, palm kernel oil, lanolin,sperm oil and Wool fat; there may further be mentioned the estersobtainable from polyglycerol and higher fatty acids containing 12 to 20carbon atoms, and the esters which result on heating polvglycerol orsorbitol with fats, for example beef taliow or coconut fat, in thepresence of caustic alkalies.

As amide amines there may be considered the products which are obtainedwhen carboxylic acids with 6 to 20 carbon atoms, such as caprylic acid,lauric acid, coconut fatty acid, palmitic acid or palm kernel fattyacid, stearic acid or oleic acid or their chlorides or methyl esters aretreated dropwise with diamines of the given formula, such asdiethylamino ethylamine, dimethylamino propylamine, methylethylaminopropylamine or diethylamino butylamine, at about 170-180 C., and thenheld for two hours in vacuum and a further two hours Without vacuum atthis temperature. The amide-amines formed are then converted into saltsat about 100-130" C., with for example sulfuric acid, phosphoric -acid,formic acid, acetic acid, or lactic acid. For the transformation of theamide amines into quaternization products, there may be employed forexample, dimethylor diethyl-sulfate, ethyl bromide, benzyl chloride,epichiorohydrin, chloracetamide or N-rnethylol chioracetamide.

The reaction of the esters with the salts or quaternization products ofthe amide amines is expediently carried out by heating for one or twohours at l130 C.

Suitable proportions of the required components may readily bedetermined from case to case by preliminary experiments. The reactionproducts can contain up to 70 percent by weight of the ester component,without the stability of the aqueous liquor produced suffering.

The process of the present invention may be applied to textile materialsof the most various kinds, e.g., on fibers or threads of wool, cotton,regenerated cellulose, cellulose acetate, polyurethanes, polyamides,polyesters, polyoleilnes, polyacrylonitrile, and/ or mixed polymers ofacrylonitrile with other vinyl compounds, or on fabrics or knitted goodsproduced thereform. The treatment of the textile materials can proceedin the customary manner, for example by agitating the materials inaqueous baths which contain the reaction products and are adjustecl asdesired to neutral, alkaline or acid reaction, for some time,expediently at 3060 C., and then drying at about 7090 C. The presentprocess may also be applied to yarns in vats and packing machines, onconical cross-wound bobbins and on piece goods of any kind, on the reeland on the foulard.

In place of water or additional to water, solvents of aliphatic oraromatic nature can also be used for making up the baths. In general,the amount of reaction product in the treatment bath is about 2-20 g./litre.

With the aid of the process of the present invention it is possible toimpart to the textile materials, in particular to those of syntheticorigin, a high serviceabili ty. Materials which tend to formelectrostatic charges are given an outstanding antistatic finish. In theproduction of yarns the treatment of the fibres with the reactionproducts according to the invention insures from every aspect a goodtextile workability, especially on the carding machine. The treatedtextile materials also possess an increased thermal stability, which hasa favourable account in various finishing treatments. White goods, whichhas been treated according to the process of the present invention,undergoes no alteration on heating and in textile materials dyed or tobe dyed, no deleterious effect is to be observed on the dying. For thetreatment of stockings or socks of polyamide threads or fibres, thosereaction products are especially suitable which were made with the useof Wool fat, lanolin, or mixtures of wool fat and tallow or of lanolinand castor oil. The stockings and socks treated with these productspossess a soft and full handle and the stockings can also be veryreadily shaped, since they are simultaneously rendered antistatic.Moreover, reaction products which are produced with the use ofquaternization products of the amide amines, are outstandingly suitablefor finishing and impregnating purposes in combination with paramn orwax emulsions containing aluminum or zirconium salts or in combinationwith water-soluble urea or melamine formaldehyde precondensates. Otherpolymeric compounds, such as polyacrylates, can also be usedconcurrently, and also fatty alcohols or their alkoxylation products aswell as mineral oils and mineral fats; thus for example an addition of3-5 percent by weight of stearyl alcohol, calculated on the reactionproduct, permits the smoothness of the textile materials treatedaccording to the invention to be significantly increased. If desired,the reaction products of the present invention can be employed also withother textile assistants, eg' with wetting agents or opticalbrighteners.

It is, moreover, to be emphasized also that the textile materialstreated according to the invention in general have no unpleasant amineodour. In order to exclude any possibility of amine odour, it isrecommended to use reaction products prepared from salts orquaternization products of amide amines in the presence of polyglycerol;such reaction products are odourless and the textile materials treatedtherewith likewise possess no undesirable amine smell.

The hitherto known agents proposed for treating textiles do not possessthe advantageous properties described, to the same extent.

The following examples serve to illustrate the invention without,however, limiting the scope thereof; the parts are by weight.

Example 1 A fabric of polyacrylonitrile fibres was agitated for 30minutes at a liquor-to-goods ratio of 20:1 at 40 C., in an aqueous bathwhich contained per litre 2.5 g. of the paste described below. Thefabric was then centrifuged and dried at 80 C. The fabric thus treatedwhich possessed no unpleasant smell, had a full and soft handle; itshowed at the same time an antistatic finish.

The paste used was prepared in the following manner:

130 parts of tallow fatty acid glycerol ester, obtained by heating 1 molof tallow and 2 mols of polyglycerol of molecular weight 170 in thepresence of 1% by weight of potassium hydroxide to 18Q200 C., werestirred for 2% hours at 100 C. with 20 parts of Vaseline and 300 partsof the acetate of an amide amine which had been produced, according tocol. 1, lines 41-59 of the specification, by heating 152 parts of afatty acid mixture which contained altogether 98% by weight of saturatedfatty acids, i.e., 62% of stearic acid, 32% of palmitic acid and 4% ofmyristic acid, to a temperature of 170180 C. in the presence of 124parts of polyglycerol of molecular weight 170 with 33 parts ofdimethyl-amino propylarnine and 18 parts of acetic acid anhydride. Thereaction product obtained was then mixed with 550 parts of warmdistilled water with addition of some glacial acetic acid. The amount ofthe diamine employed amounts to 7% by weight of the reaction product,and the molar ratio of carboxylic acid to diamine amounts to 1.7: 1. The1% aqueous solution of the 45% paste obtained possesses a pH value of4.6 to 4.9.

Example 2 Fibers of polymeric e-caprolactam (thickness 1.4/30 mm.) weretreated in the manner described in Example 1 in an aqueous bath whichcontained 1 g. per litre of the paste there described. The fibres thustreated had a soft and pleasant handle; the further working up proceededwithout trouble.

Example 3 Stocking of threads, or socks of fibers, produced frompolymeric e-caprolactam, were treated in the manner described in Example1 with an aqueous liquor containing 3 g. per litre of the pastedescribed below. The stockings and socks thus treated then possessed afull, soft and smooth handle; they no longer felt rough. At the sametime they acquired an antistatic finish.

The paste employed was produced in the following manner:

265 parts of the acetate of an amide amine prepared by reacting with oneanother 215 parts of 98% palmitic acid, 42 parts of dimethylaminopropylarnine, 10.5 parts of dimethylamino butylamine and 25 parts ofacetic acid anhydride with heating to 170-180 C. corresponding to theinstructions of the third paragraph of this specification, are stirredat 100 C. for two hour swith 620 parts of wool fat; the reaction productformed was then stirred with 1300 parts of warm distilled water to a 40%paste.

Example 4 Hanks or piece goods produced from 50 parts of polyesterfibres and 50 parts of wool, were agitated for 30 minutes at 45 C. at aliquor-to-goods ratio of :1 in an aqueous bath containing per litre 3 g.of the paste described below. After centrifuging and drying, the goodspossessed a clearly improved feel; furthermore, they were given anantistatic finish.

The paste employed was produced in the following manner:

First 260 parts of stearic acid were amidated according to theinstructions given in the third paragraph of this specification, byheating to 170-180 C., with 62 parts diethylamino ethylamine; the amideamine formed was quaternized for 1 /2 hours on the boiling water bathwith 65 parts of epichlorohydrin and 370 parts of the quaternarycompound thus obtained were then stirred at 100 C. for two hours with amixture of 435 parts of beef tallow and 435 parts of wool fat. Thereaction product formed was then stirred to a 40% paste with 1800 partsof warm distilled water. The amine content of the paste came to 5% andthe molar ratio of fatty acid to diamine in the amide amine amounted to1.67: 1.

We claim:

1. A process for treating textile materials comprising impregnating saidmaterials with an active amount of the reaction product of (A) an esterobtained by condensing a higher fatty acid containing 12-20 carbon atomswith a member selected from the group consisting of a monohydric alcoholof 412 carbon atoms, and a polyhydric alcohol containing 26 hydroxylgroups; with (B) a member selected from the group consisting of the saltand the quaternization product of an amide amine obtained by reacting adiamine of the formula wherein R and R stand independently defined asalkyl having 18 carbon atoms and n is an integer of 2-4, with a reactiveamount of (b) carboxylic acid having 6-20 carbon atoms,

the amount of diamine being not more than 8% by weight of the reactionproduct of (A) and (B).

2. The process of claim 1 wherein (B) is obtained by initially reacting1 mol of the diamine with about 11:7 mol of monocarboxylic acid.

3. The process of claim 1 comprising incorporating the reaction productof (A) and (B) into a treating bath at a concentration of about 2-20 gm.per liter of water, agitating the textile materials therein, andthereafter drying the textile materials.

4. The process of claim 1 wherein the textile materials contain asubstantial amount of at least one member of the group consisting ofregenerated cellulose, cellulose acetate, polyurethane, polyamide,polyester, poly olefine, polyacrylonitrile, and wool.

5. The process of claim 1 wherein the textile materials consistessentially of polyacrylonitrile.

6. The process of claim 1 wherein the (A) ester is obtained by heating amember selected from the group consisting of polyglycerol of molecularweight and sorbitol with fat in the presence of caustic alkali.

7. The process of claim 1 wherein the (B) amide amine is obtained byreacting carboxylic acid selected from the group consisting of caprylicacid, lauric acid, coconut fatty acid, palmitic acid, palm kernel fattyacid, stearic acid, oleic acid, and the corresponding chlorides andmethylesters, with an amine selected from the group consisting ofdiethylamino-ethylamine, dimethylamino propylamine, methylethylaminopropylamine, and diethylamino butylamine.

8. The process of claim 1 wherein the reaction product of (A) and (B) isobtained by employing the quaternization product of the amide amine inthe presence of an effective amount of polyglycerol.

9. The process of claim 5 wherein polyacrylonitrile material is agitatedin an aqueous bath containing 2-20 gm. per liter of active ingredient ina liquor-to-goods ratio of about 20:1, at about 3060 C., and thereafterdrying the material at a temperature of about 70-90 C.

10. A process for treating textile materials comprising impregnatingsaid materials with an active amount of the reaction product of (A) anester obtained by condensing a fatty acid containing 12-20 carbon atomswith a member selected from the group consisting of tallow, coconut fat,olive oil, caster oil; palm kernel oil, lanolin, sperm oil and wool fat;with (B) a member selected from the group consisting of the salt and thequaternization product of an amide amine obtained by reacting a diamineof the formula wherein R and R stand independently defined as alkylhaving 1-8 carbon atoms and n is an integer of 2-4, with a reactiveamount of (b) carboxylic acid having 6-20 carbon atoms, the amount ofdiarnine being not more than 8% by weight of the reaction product of (A)and (B).

References Cited by the Examiner UNITED STATES PATENTS 10 WILLIAM D.MARTIN, Primary Examiner.

RECHARD D. NEVIUS, Examiner.

1. A PROCESS FOR TREATING TEXTILE MATERIALS COMPRISING IMPREGNATING SAIDMATERIALS WITH AN ACTIVE AMOUNT OF THE REACTION PRODUCT OF (A) AN ESTEROBTAINED BY CONDENSING A HIGHER FATTY ACID CONTAINING 12-20 CARBON ATOMSWITH A MEMBER SELECTED FROM THE GROUP CONSISTING OF A MONOHYDRIC ALCOHOLOF 4-12 CARBON ATOMS, AND A POLYHYDRIC ALCOHOL CONTAINING 2-6 HYDROXYLGROUPS; WITH (B) A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE SALTAND THE QUATERNIZATION PRODUCT OF AN AMIDE AMINE OBTAINED BY REACTING ADIAMINE OF THE FORMULA